Redefining
Antifouling
Coatings by Dr. Geoffrey Swain,
Oceanography and Ocean Engineering,
Florida Institute of Technology,
Melbourne, FL, U.S.
This article describes alternatives to antifoulings
formulated with tributyltin.
F
or nearly a quarter century,
tributyltin-based self-polishing
copolymer antifouling paints
have provided an efficient and
economic method of ship hull
protection. Yet as we enter the
21st century, this important
technology is likely to be eliminated by
new regulations proposed by the Interna-
tional Maritime Organization.1 This has cre-
ated a major challenge for the scientific
community and the marine paint industry.
The challenge is to formulate replacement
systems that meet or exceed the perfor-
mance standards of tributyltin (TBT) self-
polishing copolymer coatings and that
comply with present and future environ-
mental regulations.
To redefine antifouling (AF) coatings,
it is useful at the outset to understand the
properties that made TBT self-polishing
coatings so successful and at the same time
environmentally unacceptable (Fig. 1).
TBT self-polishing copolymer technol-
26 SEPTEMBER 1999 / JPCL – PMC
QE II in the King
George V Dry Dock,
Southampton, UK
in 1978, with a
TBT self-polishing
copolymer antifouling
system
Photo courtesy of
the author
ogy, first patented by Milne and Hale in
19742, revolutionized the way the shipping
industry does business. A cost/benefit anal-
ysis made by Milne and Abel3 compared
TBT self-polishing coatings to the next best
non-tin alternatives that were available
prior to 1982. They estimated that these
coatings saved the world’s commercial fleet
approximately $2.4 million in direct fuel
costs, extended dry-docking, improved ship
availability, and capital savings. In addition,
there have been unspecified reductions in
fossil fuel emissions and the generation of
wastes during repainting.
One of the first ships coated with this
system was the prestigious liner QE II
(shown above). The TBT self-polishing sys-
tem was so successful that it was soon ap-
plied to much of the world’s commercial
fleets, navies, and recreational craft. Recent
estimates suggest that about 70% of the
world’s commercial fleet is protected by
TBT self-polishing coatings.4 These systems
are able to provide in excess of five years
Copyright ©1999, Technology Publishing Company
 Redefining Antifoulings

protection, an average hull roughness of

about 100 microns and complete protection
against biofouling.5
Their success is due to many factors.
First of all, tributyltin is an extremely active
biocide, about 10 times more toxic than
copper.6 This means less biocide is re-
quired to maintain a fouling-free coating.
Secondly, TBT is chemically attached to the
methyl methacrylate polymer backbone via
an organotin-ester linkage. On immersion
in sea water, the copolymer at the paint
surface reacts to release the TBT. This caus-
es the copolymer to become brittle and hy-
drophilic. Removal of the copolymer chain
causes a self-polishing action and provides
for a new supply of biocide. The coating
remains stable because the reaction is con-
fined to an extremely narrow surface layer
due to the hydrophobic properties of the
unreacted paint film.
TBT self-polishing copolymer paints
are usually formulated with cuprous oxide
pigments and other organic co-biocides.
These combinations enable paint manufac- Fig. 1 - Performance and environmental criteria of TBT self-polishing
copolymer systems and the development of environmentally friendly
turers to formulate coatings that comply antifouling technology
with the most stringent current regulations
that limit the maximum release rate to 4 pacific oyster Crassostrea gigas was ob-
µg/sq cm/day TBT (Fig. 2). served along the northwest coast of France.
Subsequent research in other parts of the
world demonstrated that organotins were
indeed impacting non-target organisms. It
Problems was shown that TBT concentrations in sea-
The success of TBT has been overshad- water as low as 20 nanograms per liter will
owed by its impact on non-target organ- cause defective shell growth in the oyster,
isms. Ships, boats, and structures coated Crassostrea gigas7 and that concentrations
with AF paints act as a point source input of 1 nanogram per liter are sufficient to dis-
of fouling-control biocides into the marine rupt the reproductive capabilities of the fe-
environment. For example, a 65,000 Gross male dog-whelk, Nucella sp., by causing a
Registered Ton container ship that is 260 m condition known as imposex.8 More recent-
long has an approximate wetted surface ly, TBT has been implicated in the deaths
area of 13,000 m.2 If it is coated with a TBT of bottle-nosed dolphins (Tursiops trunca-
self-polishing copolymer-based system with tus)9 and other marine mammals.
a biocide output of 4 µg/sq cm/day, then
the TBT input into the environment would
be about 190 kg/year. If a copper-based AF
Regulations
system was used with a minimum biocide
output of 20 µg/sq cm/day, then the cop- The first country to regulate against TBT
per input into the environment would be was France in 1982. These regulations pro-
about 950 kg/year. hibited the use of organotins from recre-
By the late 1970s, a link between the ational boats less than 25 m in length, ex-
use of TBT in AF paints and damage to the cept for aluminum-hulled vessels.

Copyright ©1999, Technology Publishing Company JPCL – PMC / SEPTEMBER 1999 27

Redefining Antifoulings
Antifoulings on U.S. Navy Ships
to Require Pollution Controls
T he U.S. Navy is an exception marine pollution control de-
to most large ship operators vice (MPCD) by December
insomuch that it has chosen 2000. An MPCD is any equip-
not to use organotin-based ment or management practice
paints on its ships.1 designed to treat, retain, or
Furthermore, it has a goal to control discharges incidental
develop environmentally to the normal operation of an
sound ships that are capable Armed Forces vessel.
of operating in compliance This policy is indicative of
with applicable state, federal, future practices and regula-
and international environmen- tions that may affect the
tal regulations and that cause worldwide fleet. ❍
no significant adverse environ-
mental impacts.
References
Section 325 of the 1996 Na- 1. R. Alberte, et al., “Biofoul-
tional Defense Authorization ing Research Needs for the
Act2 amended Section 312 of United States Navy: Pro-
the Clean Water Act to provide gram History and Goals,”
the Department of Defense Biofouling, Vol. 6, pp.
and Environmental Protection 91–95, 1992.
Agency authority to jointly es- 2. U.S. Environmental Pro-
tablish Uniform National Dis- tection Agency, Uniform
charge Standards for incidental National Discharge Stan-
liquid discharges from vessels dards for Vessels of the
of the Armed Forces. Armed Forces; Final Rule,
Antifouling coatings have Federal Register: Vol. 63,
been identified as a discharge
No. 176, September 11,
that will require some sort of 1998.
Other countries soon followed, and
by the early 1990s, similar regulations were
in force throughout the industrialized na-
tions. In addition to the ban on vessels less
than 25 m, some countries also required
that TBT output not exceed 4 µg/sq
cm/day.
It appears that these regulations have
had their desired effects, and there has
been a decline in TBT concentrations in
water, sediment, and aquatic life.10 Howev-
er, there is still concern that the use of TBT
antifoulings on commercial ships is having
adverse impact on the marine environment.
At the 42nd session of the Marine En-
vironment Protection Committee of the In-
ternational Maritime Organization (2-6
November 1998),1 a draft resolution was
approved that includes a deadline of 2008
28 SEPTEMBER 1999 / JPCL – PMC
for the complete prohibition of organotins
acting as biocides in antifouling systems on
ships and a prohibition of the application
of such systems by 1 January 2003. This
draft resolution was again debated at the
43rd session of the MEPC, and it will be
submitted to the 21st IMO Assembly in
November 1999 to be considered for
adoption.
In addition to regulations restricting
the use of biocides, paint manufacturers
may also have to comply with the amount
of hazardous air pollutants (HAP) that can
be released. In the U.S., the Environmental
Protection Agency has national emission
standards for HAP for shipbuilding and
ship repair.11 The present regulations stipu-
late that the amount of permissible volatile
organic HAP content for antifouling coat-
ings be 400 g/L or less, and it is likely that
the permissible HAP will be further re-
duced in California.
Alternative Technologies
There are many patents and ideas relating
to biofouling control, but so far, few have
been found to be practical, economic, or
effective.12-14 The environmental problems
associated with organotin-based systems
has forced a move to “environmentally
friendly antifouling” systems. This term is
not yet fully defined. In its purest sense, it
can be interpreted as meaning a system
that has no toxic components. In its broad-
est sense, it may be defined as lessening
the impact of TBT self-polishing coatings or
the return of copper and other biocides
(Fig. 1).
Return of Copper
The most common alternative biocide to
organotin is copper. This is usually added
to a paint matrix in the form of cuprous
oxide.
There are three general categories of
copper-based paints: conventional, ablative,
and self-polishing. The active life expectan-
cy of a conventional copper paint is 12-18
Copyright ©1999, Technology Publishing Company

months. This is due to inefficient leaching
characteristics, loss of copper from the sur-
face layer, and build-up of insoluble cop-
per salts (Fig. 2). Ablative systems are for-
mulated so the paint matrix saponifies at
about the same rate as the copper is re-
leased into the sea water. These systems
may achieve an active life of three or more
years. Self-polishing copper-based systems
have recently been developed15-17 with
claims of five years’ protection.
Copper on its own is vulnerable to di-
atom and algae fouling, and therefore, co-
biocides that act synergistically to enhance
the performance are required. The most
commonly found additions are diuron, tri-
azine, isothiazolin, and zinc omidine. These
compounds, however, may prove to be en-
vironmentally undesirable. Diuron and tri-
azine have been shown to be long-lasting
in the environment,18-20 and even copper
itself has come under scrutiny.21,22 Poten-
tial environmental problems and regula-
tions associated with copper-based paints
coupled with the high cost of biocide regis-
tration (more than $10 million to register a
new compound in the U.S.) increase the
need to find a non-toxic alternative for AF
protection.
Non-Stick and Fouling-Release
Surfaces
From an environmental perspective, the
non-stick and fouling-release technologies
offer the most attractive options for biofoul-
ing control.
Interest in the use of non-stick sur-
faces was stimulated by the synthesis of
polytetrafluoroethylene and other hy-
drophobic plastics in the late 1950s. It took
the scientific studies of Baier23 and Dex-
ter24 to explain the mechanism for the non-
stick phenomenon. They demonstrated that
settlement and attachment by microorgan-
isms could be related to the surface-free
energy of the substrate. They further identi-
fied a surface-free energy of 22-24
dynes/cm that produced a minimum of bio-
logical adhesive strength. These observa-
tions increased interest in the development
Copyright ©1999, Technology Publishing Company
Redefining Antifoulings
Fig. 2 - Typical performance curves for conventional and self-polishing
copolymer antifouling paints
of non-stick surfaces, and a number of flu-
orinated coatings were developed with su-
perior non-stick characteristics.25,26 Howev-
er, these coatings were unable to provide
sufficient non-stick characteristics to pre-
vent attachment by macrofouling organ-
isms. Research continues to investigate the
non-stick phenomenon, but to date, no ma-
terial has been identified that can prevent
adhesion by fouling organisms.
The only alternatives to fluorinated
compounds identified as having non-stick
and fouling-release properties are silicones.
In addition to low surface energy and low
micro-roughness, which impart non-stick
characteristics, these materials have other
properties that promote fouling release. Sil-
icones have low glass transition tempera-
tures and low modulus of elasticity. These
properties minimize mechanical locking of
biological glues, thereby increasing slip-
page and fouling release.27,28 Also, most
commercial poly (dimethylsiloxane)-based
coatings contain fluid additives. It has been
suggested that these additives create weak
surface layers and macromosaic surfaces
that further promote fouling release.29
Silicone was first reported as a foul-
ing-release coating in 1972 in a patent reg-
istered to the Battelle Institution.30 During
the 1970s and 1980s, there was only limited
interest in these coatings due to the success
of TBT self-polishing systems and to some
practical limitations of existing silicone for-
JPCL – PMC / SEPTEMBER 1999 29
Redefining Antifoulings
Fig. 3 - Barnacle adhesion strength in shear
mulations.31,32 It was only when the bio-
cide-containing coatings came under pres-
sure from environmental regulations that a
concerted effort was made to better under-
stand the mechanisms by which silicone
formulations function and to improve their
performance.
The antifouling properties of these
coatings are different from biocide-contain-
ing systems. As such, their adoption for use
may require a change in operating proce-
dures. Because they are non-toxic, they
may become fouled. This is most likely to
occur on vessels that spend extended times
in port, and under such circumstances the
coatings will require some form of in-water
hull cleaning. However, for vessels that are
continually operating at high speeds, hy-
drodynamic forces will tend to maintain the
hull in a fouling free condition.
The effectiveness of fouling-release
coatings can be measured by the ease with
which the organisms become detached. In
1994, an ASTM standard for measuring the
shear adhesion strength of barnacles was
approved.33 There is now a significant
database of barnacle adhesion strength
measurements for different species and dif-
ferent substrates (Fig. 3).
From research at Florida Institute of
Technology,34,35 a model was developed to
predict the ship speed required for self
cleaning of individual barnacles (Fig. 4).
Assuming free stream velocity and no
boundary layer, it was predicted that indi-
30 SEPTEMBER 1999 / JPCL – PMC
vidual barnacles growing on the best per-
forming silicone shown in Figure 3 would
self-clean at about 10 knots. This has been
confirmed during speed trials on a variety
of silicone formulations.
Although the hydrodynamic forces ex-
perienced by individual barnacles are easily
calculated, at present there is insufficient in-
formation to predict the water velocities re-
quired to remove other fouling types and
communities. This is due to differences in
the adhesion strengths and the drag and lift
coefficients for different fouling types as
well as the variable hydrodynamic character-
istics of boundary layer thickness and flow
patterns along a ship hull. The Florida Insti-
tute of Technology data suggests that hy-
drodynamic lift and drag forces will be in-
sufficient to remove all the fouling on the
best present-day formulations.
Full-scale ship and boat trials have
demonstrated that, under optimum operat-
ing conditions, the present generation of
silicone fouling-release coatings can pro-
vide satisfactory biofouling control. The
major advantage of these systems are that
they are non-toxic, and in additon, there is
preliminary evidence to suggest that they
provide a smoother surface, reducing skin
friction drag thus providing improved per-
formance. Disadvantages of silicones are
that they are expensive, exhibit poor adhe-
sion to the substrate, are easily damaged,
and require some form of hull cleaning.
These drawbacks can partly be addressed
by improved coating application and dock
yard practice, improved fendering and hull
care, and new technology for in-water
cleaning.
Future Technology
One possible source of new technology in-
volves natural antifouling processes. In re-
cent years, much research has been devot-
ed to this area, mainly focused on chemical
inhibition.
It has long been known that the set-
tling phases of marine organisms respond
to a diversity of chemical cues.36,37 This
has generated interest in identifying com-
Copyright ©1999, Technology Publishing Company
Redefining Antifoulings
Fig. 4 - Theoretical fouling release velocities for the barnacle Balanus eburneus
from the best silicone
pounds that might repel or inhibit fouling
organisms.38 For a compound to be consid-
ered effective, it must satisfy certain condi-
tions, including the following:
• a non-toxic mode of action;
• activity at low concentrations;
• rapid breakdown to non-polluting sub-
stances;
• effectiveness over a broad spectrum of
biofouling organisms; and
• compatibility with coating systems.
Much of the research has investigated
substances derived from organisms that are
known to remain free from fouling. For ex-
ample, extracts from bacteria,39,40
algae,41,42 sea grasses,43 corals,44
sponges,45,46 and even terrestrial plants47
have been identified as active antifouling
agents.
The identification of active com-
pounds is just one of the steps required be-
fore they can be incorporated in AF coat-
ings. A mechanism must be found by
which they can be combined with the coat-
ing matrix and supplied to the surface at a
rate sufficient to prevent fouling but with-
out wasting the compound.48 Natural
sources or synthetic analogues must be
identified to ensure supply at a reasonable
cost. In addition, the compounds must pass
rigorous scrutiny from environmental regu-
lation agencies. No natural products have
been commercialized for antifouling yet,
but researchers are hopeful of identifying
32 SEPTEMBER 1999 / JPCL – PMC
compounds that can deter fouling without
compromising the environment.
Physiological responses that reduce
biofouling are also known. For example, all
arthropods undergo periodic molts, which
will inevitably result in the shedding of old
fouled surfaces.49 Tissue sloughing in the
sponge Halichondria panicea has also been
associated with antifouling activity.50 An-
tifouling systems comprising a multi-lay-
ered surface from which the top layer
could periodically be peeled have been
proposed, but no practical system has suc-
cessfully been engineered.
Several studies have investigated the
surface properties of marine organisms
(e.g., dogfish egg cases51 and the epidermis
of sea urchins52) with respect to biofouling
control. These studies identified a variety of
interesting mechanisms, but none has been
developed into practical solutions.
From a hydrodynamic standpoint, the
three groups of greatest interest are the
cetaceans (whales and porpoises), teleosts
(bony fish), and elasmobranchs (cartilagi-
nous fish). The no-foul condition of por-
poise and killer whale skin has been at-
tributed to the outermost surface being
composed of a glycoproteinaceous material
with low surface energy.53,54
Finally, it should be remembered that
behavioral activities frequently associated
with biofouling control include spending
extended periods of time out of the water
(seals, sea lions, sea otters, etc.), migrating
into fresh water, or attending cleaning sta-
tions (shrimp on coral reefs). Parallel be-
haviors (dry boat storage, freshwater soaks,
and hull cleaning) are often practiced to
control biofouling on ships and boats.
Other Technology
It is well known that the 90:10 copper-nick-
el alloys provide excellent mechanical, cor-
rosion, and AF properties.55 They have
been successfully used as the hull plate
material on several boats56 and recently as
cladding material. With the use of modern
adhesives and polymers, copper alloys can
be applied to steel hulls and structures
Copyright ©1999, Technology Publishing Company

without creating bimetallic corrosion prob-
lems. In unpolluted sea water, this alloy ex-
hibits relatively low homogeneous corro-
sion rates, which prevent fouling, and yet it
maintains a relatively smooth surface. It is
interesting to note that a 1 millimeter-thick
copper foil homogeneously corroding at 20
µg/sq cm/day would theoretically last
about 120 years.
In some ways it is surprising that
these materials have not received wider
use. However, higher capital cost compared
to AF paints, the possibility of galvanic in-
teractions with other metal components
and cathodic protection systems, and un-
predictable performance in polluted waters
have prevented their widespread adoption.
The use of electricity, through con-
ductive coatings, has been proposed by
many researchers.57-59 By creating anodic
(halogen evolution) or cathodic (high pH)
conditions at the paint surface, organisms
can be deterred or even killed. However,
neither has been made to work for extend-
ed periods due to voltage drop across the
surface, cathodic chalk formation, and pos-
sible corrosion of the underlying steel.
Smooth surfaces generally foul less
than rough surfaces. However, no topo-
graphical surface condition has been identi-
fied that will prevent biofouling. One re-
cent idea has been the use of microfibers,60
but this has yet to be verified by long-term
field testing.
Thermal control of biofouling is well
known and practiced at some power utili-
ties.61 However, heat or cryogenic treat-
ments of ship hulls and structures are im-
practical.
Summary
Unless there is a last-minute reprieve for
TBT self-polishing copolymer materials, the
marine industry is going to be looking for
antifouling coatings with equal or better
performance.
In the short term, it would appear
that copper-based systems will re-emerge.
The most promising of these are the new
generation of copper self-polishing copoly-
Copyright ©1999, Technology Publishing Company
Redefining Antifoulings
mer paints. However, at present their long-
term performance is unsubstantiated, and it
is possible that the increased use of copper
in combination with co-biocides will prove
as equally environmentally undesirable
as TBT.
The other technology vying for mar-
ket share is fouling-release silicone. Its
non-toxic mode of action and the possibili-
ty of reduced skin friction characteristics
compared to the TBT self-polishing paints
makes it extremely attractive. However,
there are technological and operational
problems to be overcome. Improvements
are needed in coating toughness, abrasion
and cut resistance, and adhesion to the tie
coat. Operationally, these coatings may re-
quire periodic in-water cleaning, and this
will require the development of devices
that can clean without damaging the coat-
ing. Ship operators may also have to pay
greater attention to fendering and mooring
to reduce damage to the systems.
The present copper- and silicone-
based technologies do not provide systems
that are equal to or better than TBT self-
polishing paints. Therefore, research and
development is still required. This may in-
volve alternative non-stick and fouling-re-
lease materials. New ideas may be devel-
oped by studying natural AF mechanisms
or by better understanding the cues that
determine the settlement of the dispersal
phases. The idea of discovering a non-toxic
compound that deters settlement is indeed
attractive.
Many novel ideas have been pro-
posed for biofouling control. Several are
not considered environmentally acceptable;
others are not feasible with present tech-
nology; and many do not work. However,
it is important that new ideas continue to
be promoted and evaluated through peer
review and trial and error.
Finally, it should be remembered that
the development of new AF technology re-
quires a multi-disciplinary approach.
Knowledge of biological, chemical, and
physical properties as well as an under-
standing of operational requirements of the
system are all necessary to solve the age-
old problems of biofouling control. ❏
JPCL – PMC / SEPTEMBER 1999 33

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